Method for the preparation of copper (meth) acryloyloxyethyl phosphate coordination complex

ABSTRACT

A compound capable of efficiently cutting off light in the near infrared region, copper (meth)acryloyloxyethyl phosphate coordination complex, is synthesized including reacting (meth)acryloyloxyethyl phosphate and copper acetate monohydrate in water.

FIELD OF THE INVENTION

The present invention is related to a method for the preparation ofcopper (meth)acryloyloxyethyl phosphate coordination complex, which isuseful for cutting off light in the near infrared region, and inparticular to a method for the preparation of copper(meth)acryloyloxyethyl phosphate coordination complex by using water asa solvent.

BACKGROUND OF THE INVENTION

PCT application WO 99/26951 (1999) discloses a copper(meth)acryloyloxyethyl phosphate coordination complex having the formula(I), which can be used to form an optical filter film for cutting offnear-IR ray, or as a near-IR-absorbing agent in a coating composition:

R_(3−n)PO(O³¹ )_(n)Cu(II)  (I)

wherein R is CH₂═C(CH₃)COOCH₂CH₂O, and n is 1 or 2. This complex issynthesized by reacting a mixture of H₃PO₄ mono- and di-ester of2-hydroxyethyl (meth)acrylate having the formula (II) with Cu acetatemonohydrate having the following formula (III) in an organic solvent ofmethyl ethyl ketone as shown in the following reaction:

wherein R and n are defined as above. This synthesis method uses anorganic solvent detrimental to the environment and the operator,however.

SUMMARY OF THE INVENTION

The present invention provides a synthesis method for the complex havingthe above formula (I) without using an organic solvent, which comprisesreacting a H₃PO₄ ester of 2-hydroxyethyl (meth)acrylate having the aboveformula (II) with the Cu acetate monohydrate having the above formula(III) in water. The complex (I) can be obtained after evaporating waterand the resulting acetic acid. The synthesis method of the presentinvention does not use an organic solvent, and thus does not havedrawbacks caused by the organic solvent.

Preferably, a mixture of H₃PO₄ mono- and di-ester of 2-hydroxyethyl(meth)acrylate with n=1 and n=2 in the formula (II) is reacted with theCu acetate monohydrate (III) to form a mixture of complex compounds withn=1 and n=2 in the formula (I). In one of the preferred embodiments ofthe present invention said mixture of H₃PO₄ mono- and di-ester of2-hydroxyethyl (meth)acrylate having a molar ratio of the H₃PO₄ di-esterof 2-hydroxyethyl (meth)acrylate, n=1, to the H₃PO₄ mono-ester of2-hydroxyethyl (meth)acrylate, n=2, is about 0.4.

A suitable amount of the Cu acetate monohydrate (III) used in saidreaction is 1%-1000%, preferably 40-90%, based on mole of the H₃PO₄ester (II). Preferably, an excess amount of the H₃PO₄ ester (II) is usedin said reaction.

A suitable amount of water used in said reaction is 0.5-100, preferably3-4, times of weight of said H₃PO₄ ester (II).

Said reaction of the present invention may be carried out at atemperature between 0-100° C. and preferably about 25-60° C.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an infrared spectrum of a mixture of H₃PO₄ mono- and di-esterof 2-hydroxyethyl (meth)acrylate with n=1 and n=2 in the formula (II)used in the method of the present invention

FIG. 2 is an infrared spectrum of a product mixture obtained in Example1 of the present invention.

FIG. 3 is an infrared spectrum of a product mixture obtained in Example2 of the present invention.

FIG. 4 is an infrared spectrum of a product mixture obtained in controlExample 1.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention can be better understood by the following exampleswhich are illustrative only, not for limiting the scope of the presentinvention.

EXAMPLE 1

To 3 g of water in a 50-ml flask 0.78 g (3.9 mmol) of Cu acetatemonohydrate (III) and 1.12 g of a mixture of H₃PO₄ mono- and di-ester of2-hydroxyethyl (meth)acrylate in the form of light yellow oily liquidwere added. The mixture of H₃PO₄ mono- and di-ester of 2-hydroxyethyl(meth)acrylate contains 1.32 mmol of di-ester (n=1) and 3.31 mmol ofmono-ester (n=2), and has an infrared spectrum as shown in FIG. 1. Thereaction was carried at room temperature for 4 hours and at 60° C. forone hour, while the reaction mixture was stirring. A blue solid wasobtained after the reaction mixture was dried in vacuo, and an infraredspectrum thereof is shown in FIG. 2. The blue solid is believed tocontain as a major portion a mixture of complex compounds with n=1 andn=2 in the above formula (I), and unreacted H₃PO₄ mono-ester anddi-ester (II), because are all non-volatile.

EXAMPLE 2

To 3 g of water in a 50-ml flask 0.45 g (2.3 mmol) of Cu acetatemonohydrate (III) and 1.12 g of a mixture of H₃PO₄ mono- and di-ester of2-hydroxyethyl (meth)acrylate in the form of light yellow oily liquidwere added. The mixture of H₃PO₄ mono- and di-ester of 2-hydroxyethyl(meth)acrylate contains 1.32 mmol of di-ester (n=1) and 3.31 mmol ofmono-ester (n=2). The reaction was carried at room temperature for 4hours, while the reaction mixture was stirring. A blue paste wasobtained after the reaction mixture was dried in vacuo, and an infraredspectrum thereof is shown in FIG. 3. Since less amount of the Cu acetatemonohydrate (III) was used in this example in comparison with Example 1,more amount of the oily H₃PO₄ mono-ester and di-ester (II) unreacted inthe reaction mixture, causing the final product mixture being in theform of a paste.

CONTROL EXAMPLE 1

To 20 ml of methyl ethyl ketone in a 50-ml flask 0.16 g (0.8 mmol) of Cuacetate monohydrate (III) and 0.23 g of a mixture of H₃PO₄ mono- anddi-ester of 2-hydroxyethyl (meth)acrylate in the form of light yellowoily liquid were added. The mixture of H₃PO₄ mono- and di-ester of2-hydroxyethyl (meth)acrylate contains 0.27 mmol of di-ester (n=1) and0.68 mmol of mono-ester (n=2). The reaction was carried at 50° C. forone hour, while the reaction mixture was stirring. A blue solid wasobtained after the reaction mixture was dried in vacuo, and an infraredspectrum thereof is shown in FIG. 4.

It can be readily understood from examples 1-2 and control example 1that the method of the present invention uses a less amount of water inplace of an organic solvent for the same reaction, and successfullysynthesizes the same target products.

What is claimed is:
 1. A method for preparing a complex having thefollowing formula (I) comprising reacting a H₃PO₄ ester of2-hydroxyethyl (meth)acrylate having the following formula (II) with Cuacetate monohydrate having the following formula (III) in water:R_(3−n)PO(O⁻)_(n)Cu(II)  (I) wherein R is CH₂═C(CH₃)COOCH₂CH₂O, and n is1 or 2; R_(3−n)PO(OH)_(n)  (II) wherein R and n are defined as above;Cu(CH₃COO)₂.H₂O  (III).
 2. The method according to claim 1, wherein amixture of H₃PO₄ mono- and di-ester of 2-hydroxyethyl (meth)acrylatewith n=1 and n=2 in the formula (II) is reacted with the Cu acetatemonohydrate (III) to form a mixture of complex compounds with n=1 andn=2 in the formula (I).
 3. The method according to claim 2, wherein saidmixture of H₃PO₄ mono- and di-ester of 2-hydroxyethyl (meth)acrylatehaving a molar ratio of the H₃PO₄ di-ester of 2-hydroxyethyl(meth)acrylate, n=1, to the H₃PO₄ mono-ester of 2-hydroxyethyl(meth)acrylate, n=2, is about 0.4.
 4. The method according to claim 1,wherein an amount of the Cu acetate monohydrate (III) used in saidreaction is 1%-1000%, based on mole of the H₃PO₄ ester (II).
 5. Themethod according to claim 4, wherein the amount of the Cu acetatemonohydrate (III) used in said reaction is 40-90%, based on mole of theH₃PO₄ ester (II).
 6. The method according to claim 1, wherein an amountof water used in said reaction is 0.5-100 times of weight of said H₃PO₄ester (II).
 7. The method according to claim 6, wherein said amount ofwater used in said reaction is 3-4 times of weight of said H₃PO₄ ester(II).
 8. The method according to claim 1, wherein said reaction iscarried out at a temperature between 0 to 100° C.
 9. The methodaccording to claim 8, wherein said reaction is carried out at atemperature between 25 to 60° C.